DE4436498A1 - Process for the preparation of a monolithium acetylide-ammonia complex - Google Patents
Process for the preparation of a monolithium acetylide-ammonia complexInfo
- Publication number
- DE4436498A1 DE4436498A1 DE4436498A DE4436498A DE4436498A1 DE 4436498 A1 DE4436498 A1 DE 4436498A1 DE 4436498 A DE4436498 A DE 4436498A DE 4436498 A DE4436498 A DE 4436498A DE 4436498 A1 DE4436498 A1 DE 4436498A1
- Authority
- DE
- Germany
- Prior art keywords
- ammonia
- ammonia complex
- acetylide
- complex
- acetylene
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Withdrawn
Links
- 238000000034 method Methods 0.000 title claims description 14
- YZKAYZCWVWOZEA-UHFFFAOYSA-N N.C#[C-].[Li+] Chemical compound N.C#[C-].[Li+] YZKAYZCWVWOZEA-UHFFFAOYSA-N 0.000 title claims description 9
- 238000002360 preparation method Methods 0.000 title claims description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 23
- 238000006243 chemical reaction Methods 0.000 claims description 14
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 claims description 13
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 claims description 13
- 229910021529 ammonia Inorganic materials 0.000 claims description 12
- AFRJJFRNGGLMDW-UHFFFAOYSA-N lithium amide Chemical compound [Li+].[NH2-] AFRJJFRNGGLMDW-UHFFFAOYSA-N 0.000 claims description 11
- 150000001299 aldehydes Chemical class 0.000 claims description 3
- 150000002576 ketones Chemical class 0.000 claims description 3
- FUSUHKVFWTUUBE-UHFFFAOYSA-N buten-2-one Chemical compound CC(=O)C=C FUSUHKVFWTUUBE-UHFFFAOYSA-N 0.000 description 6
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- BZLVMXJERCGZMT-UHFFFAOYSA-N Methyl tert-butyl ether Chemical compound COC(C)(C)C BZLVMXJERCGZMT-UHFFFAOYSA-N 0.000 description 4
- ARNWQMJQALNBBV-UHFFFAOYSA-N lithium carbide Chemical compound [Li+].[Li+].[C-]#[C-] ARNWQMJQALNBBV-UHFFFAOYSA-N 0.000 description 4
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- VWWMOACCGFHMEV-UHFFFAOYSA-N dicarbide(2-) Chemical compound [C-]#[C-] VWWMOACCGFHMEV-UHFFFAOYSA-N 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- PSQYTAPXSHCGMF-BQYQJAHWSA-N β-ionone Chemical compound CC(=O)\C=C\C1=C(C)CCCC1(C)C PSQYTAPXSHCGMF-BQYQJAHWSA-N 0.000 description 2
- SFEOKXHPFMOVRM-UHFFFAOYSA-N (+)-(S)-gamma-ionone Natural products CC(=O)C=CC1C(=C)CCCC1(C)C SFEOKXHPFMOVRM-UHFFFAOYSA-N 0.000 description 1
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- 150000000476 acetylides Chemical group 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 150000001728 carbonyl compounds Chemical class 0.000 description 1
- 235000021466 carotenoid Nutrition 0.000 description 1
- 150000001747 carotenoids Chemical class 0.000 description 1
- 238000003776 cleavage reaction Methods 0.000 description 1
- 239000013065 commercial product Substances 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- 229930002839 ionone Natural products 0.000 description 1
- 150000002499 ionone derivatives Chemical class 0.000 description 1
- 229910000103 lithium hydride Inorganic materials 0.000 description 1
- XDGBLAFHHLKULM-UHFFFAOYSA-N lithium;ethyne Chemical compound [Li+].[C-]#C XDGBLAFHHLKULM-UHFFFAOYSA-N 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 229910000069 nitrogen hydride Inorganic materials 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 238000005057 refrigeration Methods 0.000 description 1
- 230000007017 scission Effects 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 238000010626 work up procedure Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C403/00—Derivatives of cyclohexane or of a cyclohexene or of cyclohexadiene, having a side-chain containing an acyclic unsaturated part of at least four carbon atoms, this part being directly attached to the cyclohexane or cyclohexene or cyclohexadiene rings, e.g. vitamin A, beta-carotene, beta-ionone
- C07C403/06—Derivatives of cyclohexane or of a cyclohexene or of cyclohexadiene, having a side-chain containing an acyclic unsaturated part of at least four carbon atoms, this part being directly attached to the cyclohexane or cyclohexene or cyclohexadiene rings, e.g. vitamin A, beta-carotene, beta-ionone having side-chains substituted by singly-bound oxygen atoms
- C07C403/08—Derivatives of cyclohexane or of a cyclohexene or of cyclohexadiene, having a side-chain containing an acyclic unsaturated part of at least four carbon atoms, this part being directly attached to the cyclohexane or cyclohexene or cyclohexadiene rings, e.g. vitamin A, beta-carotene, beta-ionone having side-chains substituted by singly-bound oxygen atoms by hydroxy groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/36—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring increasing the number of carbon atoms by reactions with formation of hydroxy groups, which may occur via intermediates being derivatives of hydroxy, e.g. O-metal
- C07C29/38—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring increasing the number of carbon atoms by reactions with formation of hydroxy groups, which may occur via intermediates being derivatives of hydroxy, e.g. O-metal by reaction with aldehydes or ketones
- C07C29/42—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring increasing the number of carbon atoms by reactions with formation of hydroxy groups, which may occur via intermediates being derivatives of hydroxy, e.g. O-metal by reaction with aldehydes or ketones with compounds containing triple carbon-to-carbon bonds, e.g. with metal-alkynes
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F1/00—Compounds containing elements of Groups 1 or 11 of the Periodic Table
- C07F1/02—Lithium compounds
-
- C—CHEMISTRY; METALLURGY
- C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
- C12C—BEER; PREPARATION OF BEER BY FERMENTATION; PREPARATION OF MALT FOR MAKING BEER; PREPARATION OF HOPS FOR MAKING BEER
- C12C11/00—Fermentation processes for beer
- C12C11/02—Pitching yeast
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2601/00—Systems containing only non-condensed rings
- C07C2601/12—Systems containing only non-condensed rings with a six-membered ring
- C07C2601/16—Systems containing only non-condensed rings with a six-membered ring the ring being unsaturated
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Life Sciences & Earth Sciences (AREA)
- Food Science & Technology (AREA)
- Health & Medical Sciences (AREA)
- Biochemistry (AREA)
- Bioinformatics & Cheminformatics (AREA)
- General Engineering & Computer Science (AREA)
- General Health & Medical Sciences (AREA)
- Genetics & Genomics (AREA)
- Mycology (AREA)
- Wood Science & Technology (AREA)
- Zoology (AREA)
- Microbiology (AREA)
- Materials Engineering (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
Die vorliegende Erfindung betrifft ein verbessertes Verfahren zur Herstellung eines Monolithiumacetylid-Ammoniak-Komplexes durch Umsetzung von Lithiumamid und Acetylen in Ammoniak. Weiterhin be trifft sie die Verwendung des so hergestellten Acetylidkomplexes zur Ethinylierung α,β-ungesättigter Ketone und Aldehyde.The present invention relates to an improved method for Preparation of a monolithium acetylide-ammonia complex by Conversion of lithium amide and acetylene into ammonia. Continue to be it meets the use of the acetylide complex thus produced for the ethynylation of α, β-unsaturated ketones and aldehydes.
Die CH-A 642 936 beschreibt die Herstellung eines Monolithiumace tylid-Ammoniak-Komplexes aus Lithiumamid und Acetylen. Lithium amid wird dazu in einem inerten organischen Lösungsmittel suspen diert und bei unter 30°C, bevorzugt unter 10°C, mit Acetylen ver setzt. Diese Herstellweise kann nicht völlig befriedigen, da sich in den organischen Lösungsmitteln Dilithiumacetylid (Lithiumcar bid) bildet, das unreaktiv ist und aus der Lösung ausfällt. Wei terhin sind die Reaktionszeiten relativ lang. Das Lithiumamid reagiert unter den genannten Bedingungen außerdem nicht vollstän dig ab, was in Folgereaktionen mit α,β-ungesättigten Carbonyl verbindungen zu deren unerwünschter Polymerisation führen kann.CH-A 642 936 describes the production of a monolithium ace tylid-ammonia complex from lithium amide and acetylene. Lithium amide is suspended in an inert organic solvent diert and at below 30 ° C, preferably below 10 ° C, with acetylene ver puts. This method of production can not be completely satisfactory, since in organic solvents dilithium acetylide (Lithiumcar bid) that is unreactive and fails from solution. Wei the response times are relatively long. The lithium amide does not fully respond under the conditions mentioned dig, what in subsequent reactions with α, β-unsaturated carbonyl compounds can lead to their undesirable polymerization.
Aus Chimia 40 (1986) 323 ist bekannt, daß der Monolithiumacety lid-Ammoniak-Komplex thermisch nicht stabil ist und in Lithium carbid, Acetylen und Ammoniak zerfällt.From Chimia 40 (1986) 323 it is known that the monolithium acety lid-ammonia complex is thermally unstable and in lithium carbide, acetylene and ammonia disintegrates.
Es bestand die Aufgabe, ein Verfahren bereitzustellen, daß die genannten Nachteile bekannter Verfahren vermeidet.The object was to provide a method that mentioned disadvantages of known methods avoided.
Demgemäß wurde das eingangs definierte Verfahren gefunden, das dadurch gekennzeichnet ist, daß man die Umsetzung bei -10°C bis 30°C vornimmt.Accordingly, the process defined at the outset was found, the is characterized in that the reaction at -10 ° C to 30 ° C.
Beim erfindungsgemäßen Verfahrensprodukt handelt es sich wahr scheinlich um den Komplex LiC≡CH·NH₃.The process product according to the invention is true apparently around the complex LiC≡CH · NH₃.
Erfindungsgemäß wird Lithiumamid mit Acetylen umgesetzt. Lithium amid ist als Handelsprodukt erhältlich oder kann beispielsweise durch Umsetzung von Lithiumhydrid mit Ammoniak unter Wasser stoffabspaltung hergestellt werden. Das erfindungsgemäß zu ver wendende Acetylen ist bevorzugt acetonfrei, um unerwünschte Nebenreaktionen zu verhindern. Es kann mit inerten Gasen wie Stickstoff oder Argon verdünnt werden; bevorzugt wird es aber un verdünnt eingesetzt. According to the invention, lithium amide is reacted with acetylene. Lithium amide is available as a commercial product or can, for example by reacting lithium hydride with ammonia under water cleavage can be produced. To ver according to the invention Turning acetylene is preferably acetone-free to avoid undesirable To prevent side reactions. It can be used with inert gases such as Dilute nitrogen or argon; but it is preferred used diluted.
Im allgemeinen können 1 bis 10 mol Acetylen pro Mol Lithiumamid verwendet werden, bevorzugt sind jedoch 1 bis 3 mol.In general, 1 to 10 moles of acetylene per mole of lithium amide are used, but 1 to 3 mol are preferred.
Das erfindungsgemäße Verfahren wird in Ammoniak als Lösungsmittel ausgeführt. In der Regel werden 7 bis 30 mol Ammoniak pro Mol Lithiumamid verwendet.The inventive method is in ammonia as a solvent executed. As a rule, 7 to 30 moles of ammonia per mole Lithium amide used.
In einer bevorzugten Ausführungsform wird zunächst Lithiumamid mit Ammoniak versetzt. Dann wird unter Rühren Acetylen zum Reak tionsansatz gegeben.In a preferred embodiment, lithium amide is used first mixed with ammonia. Then, with stirring, acetylene becomes a reak given approach.
Da sich das Acetylen relativ schnell im Ammoniak löst und abre agiert, kann es so zugegeben werden, daß der Druck während der Acetylen-Zugabe praktisch konstant bleibt. Es hat sich als vor teilhaft erwiesen, die Reaktion unter dem Eigendruck des Ammo niaks bei der gewählten Reaktionstemperatur vorzunehmen, was je nach Reaktionstemperatur einem Druck von ca. 3 bis 15 bar ent spricht.Because the acetylene dissolves and breaks down relatively quickly in the ammonia acts, it can be added so that the pressure during the Acetylene addition remains practically constant. It turned out to be partially proved the reaction under the pressure of the ammo niaks at the chosen reaction temperature, which ever after the reaction temperature, a pressure of about 3 to 15 bar speaks.
Die Reaktionstemperatur beträgt -10 bis 30°C, bevorzugt 0 bis 20°C.The reaction temperature is -10 to 30 ° C, preferably 0 to 20 ° C.
Das erfindungsgemäße Verfahren kann in Rührkesseln oder Druck behältern ausgeübt werden.The process according to the invention can be carried out in stirred tanks or in pressure containers are exercised.
Die Reaktion zum Monolithiumacetylid-Ammoniak-Komplex ist in der Regel nach wenigen Minuten beendet. Es hat sich als zweckmäßig erwiesen, solche Lösungen des Acetylidkomplexes herzustellen, die ca. 1- bis 3-molar am Verfahrensprodukt sind.The reaction to the monolithium acetylide ammonia complex is in the Usually ended after a few minutes. It has come in handy proven to prepare such solutions of the acetylide complex that are about 1 to 3 molar on the process product.
Das erfindungsgemäße Verfahren erlaubt eine praktisch quantita tive Acetylenumsetzung, wobei sich Lithiumcarbid als Nebenprodukt nicht nachweisen läßt. Es ist technisch äußerst wünschenswert, die Reaktion bei den genannten Temperaturen ablaufen zu lassen, da dazu keine teueren Kälteaggregate erforderlich sind. Wenn bei Temperaturen unter Raumtemperatur gearbeitet werden soll, können diese Temperaturen mit Kältesolen, wie sie in chemischen Betrie ben üblicherweise vorhanden sind, in einfacher Weise eingestellt werden.The method according to the invention allows a practically quantitative tive acetylene conversion, with lithium carbide as a by-product cannot be demonstrated. It’s technically extremely desirable letting the reaction proceed at the temperatures mentioned, since no expensive refrigeration units are required. If at Temperatures below room temperature can be worked these temperatures with cold brines, as in chemical companies ben usually exist, set in a simple manner will.
Der erfindungsgemäß hergestellte Monolithiumacetylid-Ammoniak- Komplex kann in an sich bekannter Weise weiter umgesetzt werden. Die den Komplex enthaltene Ammoniaklösung kann unter Verdampfen des Ammoniaks entspannt werden. Der so erhaltene Komplex kann dann in einem inerten organischen Lösungsmittel wie Toluol, Tetrahydrofuran oder Methyl-tert.-butylether aufgenommen werden und mit α,β-ungesättigten Aldehyden oder Ketonen wie Methylvinyl keton oder Aceton unter Addition der Acetylidgruppe umgesetzt werden. Nach hydrolytischer Aufarbeitung erhält man so wertvolle Zwischenprodukte für Carotinoidsynthesen (s. CH-A 642 936).The monolithium acetylide ammonia Complex can be implemented in a manner known per se. The ammonia solution contained in the complex can evaporate of ammonia can be relaxed. The complex thus obtained can then in an inert organic solvent such as toluene, Tetrahydrofuran or methyl tert-butyl ether are added and with α, β-unsaturated aldehydes or ketones such as methyl vinyl ketone or acetone reacted with addition of the acetylide group will. After hydrolytic work-up you get valuable Intermediates for carotenoid synthesis (see CH-A 642 936).
In einen 150 l Autoklaven (Nenndruck 25 bar) wurden zunächst 8 kg (348 mol) Lithiumamid und dann 100 l flüssiger Ammoniak gegeben. Es stellte sich ein Druck von ca. 8 bar ein.8 kg were initially placed in a 150 l autoclave (nominal pressure 25 bar) (348 mol) lithium amide and then 100 l of liquid ammonia. A pressure of approx. 8 bar was established.
Unter Rühren wurden 8 m³ (357 mol) Acetylen in den Ansatz gepreßt. Nach 15 Minuten wurde der Autoklav entspannt und der entstandene Monolithiumacetylid-Ammoniak-Komplex in 100 l Methyl-tert.-butyl ether suspendiert. Lithiumcarbid war nicht nachweisbar.8 m³ (357 mol) of acetylene were pressed into the mixture with stirring. After 15 minutes, the autoclave was released and the resulting one Monolithium acetylide ammonia complex in 100 l of methyl tert-butyl ether suspended. Lithium carbide was undetectable.
Bei -5°C wurden danach 22,5 kg Methylvinylketon in die Suspension gegeben. Nach Hydrolyse und Destillation erhielt man 3-Hydroxy-3-methyl-penten-4-in-1 in 87% Ausbeute.At -5 ° C, 22.5 kg of methyl vinyl ketone were then in the suspension given. After hydrolysis and distillation, one obtained 3-Hydroxy-3-methylpentene-4-in-1 in 87% yield.
Analog zu Beispiel 1 wurde die Synthese des Monolithiumacetylid Ammoniak-Komplexes bei 0°C und einem Eigendruck von 2,5 bar durch geführt.The synthesis of monolithium acetylide was analogous to Example 1 Ammonia complex at 0 ° C and an autogenous pressure of 2.5 bar guided.
Die nachfolgende Umsetzung mit Methylvinylketon ergab 89% Aus beute.The subsequent reaction with methyl vinyl ketone gave 89% Aus prey.
Der Monolithiumacetylid-Ammoniak-Komplex wurde analog zu Bei spiel 1 hergestellt.The monolithium acetylide ammonia complex was analogous to Bei game 1 made.
Die nachfolgende Umsetzung mit 20,3 kg (350 mol) Aceton ergab 98% Methylbutinol.The subsequent reaction with 20.3 kg (350 mol) of acetone gave 98% methyl butinol.
Der Monolithiumacetylid-Ammoniak-Komplex wurde analog zu Bei spiel 1 hergestellt.The monolithium acetylide ammonia complex was analogous to Bei game 1 made.
Die nachfolgende Umsetzung mit 70,7 kg (350 mol) β-Ionon ergab 94% ethinyliertes Ionon.The subsequent reaction with 70.7 kg (350 mol) of β-ionone gave 94% ethynylated ionone.
Claims (3)
Priority Applications (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE4436498A DE4436498A1 (en) | 1994-10-13 | 1994-10-13 | Process for the preparation of a monolithium acetylide-ammonia complex |
| DE59509999T DE59509999D1 (en) | 1994-10-13 | 1995-10-06 | Process for the preparation of a monolithium acetylide ammonia complex |
| EP95115743A EP0707008B1 (en) | 1994-10-13 | 1995-10-06 | Process for the preparation of a monolithium-acetylide-ammonia complex |
| JP7263058A JPH08176037A (en) | 1994-10-13 | 1995-10-11 | Method of preparing monolithium acetylide/ammonia complex and method of ethynilating alpha,beta-unsaturated ketone andaldehyde |
| US08/542,188 US5689017A (en) | 1994-10-13 | 1995-10-12 | Preparation of a monolithium acetylide/ammonia complex |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE4436498A DE4436498A1 (en) | 1994-10-13 | 1994-10-13 | Process for the preparation of a monolithium acetylide-ammonia complex |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| DE4436498A1 true DE4436498A1 (en) | 1996-04-18 |
Family
ID=6530607
Family Applications (2)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| DE4436498A Withdrawn DE4436498A1 (en) | 1994-10-13 | 1994-10-13 | Process for the preparation of a monolithium acetylide-ammonia complex |
| DE59509999T Revoked DE59509999D1 (en) | 1994-10-13 | 1995-10-06 | Process for the preparation of a monolithium acetylide ammonia complex |
Family Applications After (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| DE59509999T Revoked DE59509999D1 (en) | 1994-10-13 | 1995-10-06 | Process for the preparation of a monolithium acetylide ammonia complex |
Country Status (4)
| Country | Link |
|---|---|
| US (1) | US5689017A (en) |
| EP (1) | EP0707008B1 (en) |
| JP (1) | JPH08176037A (en) |
| DE (2) | DE4436498A1 (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2772023B1 (en) * | 1997-12-08 | 2000-02-11 | Univ Rennes | PROCESS FOR THE PREPARATION OF TRUE ACETYLENIC COMPOUNDS BY REACTION OF LITHIUM MONOACETYLIDE WITH AN ELECTROPHILIC REAGENT |
| US20250059118A1 (en) * | 2021-12-17 | 2025-02-20 | Dsm Ip Assets B.V. | Process for ethynylating specific alpha, beta-unsaturated ketones |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3557220A (en) * | 1966-09-06 | 1971-01-19 | Lithium Corp | Ethynylation of aldehydes and ketones |
| US3445534A (en) * | 1966-09-06 | 1969-05-20 | Lithium Corp | Ethynylating agent and preparation thereof |
| US3441621A (en) * | 1966-12-30 | 1969-04-29 | Air Reduction | Process for the preparation of alkali metal acetylides |
| CH642936A5 (en) * | 1979-10-19 | 1984-05-15 | Hoffmann La Roche | AETHINYLATION ALPHA, BETA-UNSATURATED KETONE. |
| US5068368A (en) * | 1990-05-10 | 1991-11-26 | Cyprus Foote Mineral Company | Stabilized lithium acetylide and reactions therewith |
-
1994
- 1994-10-13 DE DE4436498A patent/DE4436498A1/en not_active Withdrawn
-
1995
- 1995-10-06 DE DE59509999T patent/DE59509999D1/en not_active Revoked
- 1995-10-06 EP EP95115743A patent/EP0707008B1/en not_active Revoked
- 1995-10-11 JP JP7263058A patent/JPH08176037A/en active Pending
- 1995-10-12 US US08/542,188 patent/US5689017A/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| EP0707008A2 (en) | 1996-04-17 |
| US5689017A (en) | 1997-11-18 |
| EP0707008B1 (en) | 2002-01-16 |
| EP0707008A3 (en) | 1999-03-17 |
| DE59509999D1 (en) | 2002-02-21 |
| JPH08176037A (en) | 1996-07-09 |
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